Naphthene-hydrocarbon-aminoanthrapyrimidines



Patented July 12, 1938 UNITED STATES ATENT OFFICE Karl Koeberle and Otto Schliohting, Ludwigshafen-on-thc-Rhine,

Germany, assignors to General Aniline Works, Inc., New York, N. Y., a corporation of Delaware No Drawing. Application February 3, 1937, Se-

rial No. 123,862. In Germany February 13,

Claims.

The present invention relates to organic compounds of high molecular weight.

We have found that organic compounds of high molecular weight having the following composi- 5 tion:

M(AX)n in which M stands for the radical of a compound having at least 3 condensed rings, A is an oxygen, sulphur, selenium, or nitrogen bridge which may also be part of a nucleus of the compound M, X is the radical of a hydrocarbon of the naphthene series, and n is a whole number, are advantageously suitable for a great variety of uses.

The said new compounds may be prepared for example by causing compounds which contain a radical X at least once to react with cyclic compounds containing at least three nuclei, the starting materials being so chosen that one of them contains at least one reactive hydrogen or metal atom attached to oxygen, sulphur, selenium or nitrogen, and the other contains at least one atom or atomic group which allows of the replacement.

of the said reactive hydrogen or metal atom by the radical of the other initial material; or compounds of the composition M(AX)n, in which M is the radical of any cyclic compound, may be converted into compounds of the composition given above by the joining on of rings to M.

As initial materials for the process may be mentioned for example hydroxy, mercapto, seleno and primary and secondary amino compounds of the naphthene series. These compounds, if desired in the form of their salts, are caused to react with cyclic compounds containing at least three nuclei and containing exchangeable atoms or atomic groups. As such may be mentioned for example hydroxyl, halogen, nitro, sulphonic acid, acyloxy and alkoxy compounds of the acenaphthene, naphthalic acid anhydride, naphthalimide, anthracene, phenanthrene, pyrene, chrysene, carbazole, anthraquinone, azanthraquinone, benzanthraquinone, dibenzanthrone, isodibenzanthrone, perylene, dibenzoylperylene, perylene dicarboxylic acid ester, anthanthrone, anthanthrene,'pyranthrone, benzanthrone, dibenzanthronyl, pyridinoanthraquinone, azabenzanthrone,anthraquinoneacridone, anthraquinoneazine, coeramidonine, anthrapyrimidine, anthrapyrimidone, anthrapyridine, anthrapyridone, coeroxene, coerthiene, oxazine, thiazine, pyrone, pyrazolanthrone and pyrroloanthrone series.

Furthermore compounds containing at least one reactive hydrogen or metal atom attached to an oxygen, sulphur, selenium or nitrogen atom may be caused to react with compounds of the composition XY in which Y is a halogen atom, some other exchangeable atom or an exchangeable atomic group. When the radicle Y is present more than once, the exchange may be carried out a corresponding number of times whereby the radicals taking the place of Y may be different from each other. For example hydroxy, mercapto, seleno or amino compounds of anthraquinones, benzanthrones, anthanthrones, dibenzpyrenequinones and isodibenzpyrenequinones, perylenes, fluorenones, carbazoles, azabenzanthrones or other compounds containing at least three nuclei may be caused to react in which the radical having the exchangeable hydrogen or metal atom is present attached to a radical of a compound of the class specified in the preceding paragraph.

The reaction of the initial materials may frequently be effected by simple heating. In many cases it is preferable to employ diluents and/or agents facilitating the reaction and/or agents which bind acids. As diluents may be mentioned for example high-boiling hydrocarbons, alcohols, ketones, halogen-hydrocarbons and nitro-hydrocarbons. In some cases it is advantageous to carry out the reaction in a closed vessel.

In the reaction of halogen compounds of the said kind, for example, it is preferable to add diluents of high boiling point and/or copper or copper compounds and/or substances which bind acids. The reaction of hydroxy compounds is frequently facilitated by the addition of reducing agents, as for example sodium sulphite. In the reaction of nitro compounds it is advantageous to add substances which render any nitrous acid formed non-injurious.

The new compounds thus obtainable are usually obtained in good yields and in a very pure form. If desired they may be purified by the usual methods, as for example by crystallization, boiling with solvents, sublimation or by way of their salts with strong acids. Generally speaking they have a comparatively low melting point and are soluble very Well in organic solvents, in particular in hydrocarbons and other substances which are not miscible, or which are only miscible with difficulty, with water. They may be used as dyestuffs, for the preparation of dyestuffs and for a number of other industrial purposes. Thus they are frequently especially suitable for dyeing and/ or rendering fluorescent artificial resins, hydrocarbons, paraffin waxes, oils, waxes, rubber and similar natural and synthetic plastic masses as well as cellulose esters and ethers. The solubility of the compounds, and therefore their usefulness as additions to hydrocarbons and other similar compounds, increases with increasing molecular size of the naphthene radicals and with the number of these radicals. Finally especially readily soluble compounds may be obtained by so selecting the initial materials that the final substance contains not only the naphthene radical but also radicals of aliphatic or hydroaromatic hydrocarbons in any combination.

The following examples will further illustrate how the said invention may be carried out in practice but the invention is not restricted to these examples. The parts are by weight.

Example 1 A mixture of 10 parts of 2-hydroxy-1.9-anthra pyrimidine and 20 parts of naphthenylamine is heated at from 180 to 200 C. in a stirring vessel until initial material is no longer present. After cooling to about 80 C., the mixture is diluted with 100 parts of methanol and the Z-naphthenylamino-1.9-anthrapyrimidine which has separated in the cold is filtered ofi by suction and washed with methanol. It is an orange-red powder which dissolves in concentrated sulphuric acid giving a red-violet coloration which changes to red upon the addition of formaldehyde and to orange-red through blue-violet on the addition of water. In cold alcohol it is rather difiicultly soluble and in hot alcohol more readily soluble giving a yellow coloration and a green-yellow fluorescence. It is scarcely soluble in glacial acetic acid but dissolves readily in acetone and very readily in ether, benzene, paraffin oil and other hydrocarbons giving a yellow coloration and a strong green fluorescence. The yield is about the calculated yield..

If 2-hydroxy-1.9-anthrapyrimidine be heated to about 200 C. in a closed vessel with hexahydrobenzylamine in the presence of butyl alcohol, Z-hexahydrobenzylamino 1.9 anthrapyrimidine is obtained in the form of a red-yellow powder which dissolves readily in benzene, paraffin and other hydrocarbons as Well as in mineral oils and imparts a yellowish green fluorescence to these substances.

Instead of 2-hydroxyanthrapyrimidine, other anthrapyrimidines having reactive atoms or atomic groups, as for example halogen-, nitroor alkoxy-anthrapyrimidines or anthrapyrimidine sulphonic acids which contain such atoms or atomic groups in the 2-, 3-, 4-, 5-, 6-, 7-, 8- or PyC-position, may be reacted with amines of the said kind. In all cases final products are obtained which dissolve readily in hydrocarbons, which in part are strongly colored and which in part also fluoresce vividly.

In addition to exchangeable atoms or atomic groups, the initial materials may also contain further radicals, as for example alkyl, hydroxyalkyl, cyano, carbonamide, carboxylic acid or carboxylic acid ester groups. For example from 2-hydroxy-PyC-octodecyl- 1.9 anthrapyrimidine and naphthenylamine there is obtained Z-naphthenylamino-PyC-octodecyl 1.9 anthrapyrimidine which is extremely readily soluble in hydrocarbons. The solutions have a strong green-yellow fluorescence.

From 2 hydroxy 1.9 anthrapyrimidine and naphthenyl bromide there is obtained the 2- naphthenyl ether and from Z-mercaptoor 2- seleno-1.9-anthrapyrimidines the corresponding thio or seleno ethers of the anthrapyrimidine series. They are yellow-red powders which also di'ssolve comparatively readily in organic solvents, in some cases with fluorescence.

If Z-amino 1.9 anthrapyrimidine be heated with naphthenyl bromide, a compound is formed which has properties similar to 2-naphthenylamino-l.9-anthrapyrmidine.

Example 2 A mixture of 12 parts of methoxypyranthrone (prepared by the methylation of hydroxypyranthrone which is obtained from aminopyranthrone by diazotization and exchange of the diazo group by a hydroxy group) and 50 parts of naphthenylamine is heated to boiling in a stirring vessel until the color of the reaction mixture has become pure yellow. After cooling, the whole is taken up in dioxane, slight amounts of insoluble material are filtered off and methanol is added to the filtrate. The precipitated compound is filtered oil by suction and washed with methanol. The naphthenylamino-pyranthrone thus obtained is an orange powder which dissolves in concentrated sulphuric acid giving a blue coloration with a violet-red fluorescence. It is more diflicultly soluble in alcohol and glacial acetic acid giving a yellow coloration with a green fluorescence. It is more readily soluble in acetone and very readily in ether, benzene and mineral oils giving a yellow coloration and a strong green fluorescence.

If hydroxypyranthrone be used instead of methoxypyranthrone, the same compound is obtained.

Compounds having similar properties are obtained from methoxyanthanthrones, dihydroxyanthanthrones, hydroxy, alkoxy or aryloxy compounds of allo-ms-naphthodianthrones, ms-anthradianthrones, dibenzanthrones, isodibenzanthrones, benzanthraquinones, benzanthrones, dibenzpyrenequinones, isodibenzpyrenequinones, anthraquinoneazines, flavanthrones, anthraquinoneacridones, pyridinoanthraquinones and their reduction products.

Instead of the hydroxy compounds, acetoxy or nitro compounds may also be employed.

Compounds which are readily soluble and which in part fluoresce strongly are also obtained with hexahydrobenzylethylamine or hexahydrophenylethylamine from the said or similar substances.

If mercaptopyranthrone be heated in alkaline solution with naphthenyl chloride, the corresponding thio ether is obtained in a good yield; from selenopyranthrones, the corresponding seleno compounds are obtained.

Similarly from hydroxy-azapyranthrones, as for example from hydroxy-Bz-monoazapyranthrones or hydroxy-BzBz'-diazapyranthrones by heating with naphthenylamine the corresponding naphthenyl aminoazapyranthrones are obtained and by heating with naphthenyl bromide the corresponding naphthenyl others are obtained. Similarly from mercapto compounds of azapyranthrones and naphthenyl bromide the corresponding thio ethers are obtained and from the alkali selenides of azapyranthrones and naphthenyl halides the corresponding selenium compounds are obtained.

Example 3 A mixture of 33 parts of 2-bromo-4-amino-L9- anthrapyrimidine, 37 parts of naphthenylamine, 10 parts of sodium acetate and 150 parts of amyl alcohol is heated to boiling in a stirring vessel until initial material is no longer present. The mixture is then diluted at about 80 C. with 150 parts of methanol and, after cooling, the yellow crystal pulp formed is filtered oil by suction and the residue washed first with methanol and then with Water. ll-amino-2-naphthenylamino-1.9- anthrapyrimidine is thus obtained as a greenish yellow crystal powder which melts at from 170 to 175 C. It dissolves in concentrated sulphuric acid giving a red coloration which changes to violet-red on the addition of formaldehyde. It is soluble in organic solvents, in particular in ether, benzene and mineral oils giving a yellow color and a powerful yellow-green fluorescence.

If 2-hydroxy-4-amino-1.9-anthrapyrimidine or l-amino-1.9-anthrapyrimidine-2-sulphonic acid be used instead of 2-bromo-4-amino-1.Q-anthrapyrimidine, a compound having similar properties is obtained.

From the acylamines of 2-chloror Z-brom-- amino-1.9-anthrapyrimidine and stearic, oleic, lauric, abietic, hexahydrobenzoic acid and naphthenylamine, there are obtained specially readily soluble, very vividly-fluorescing 2-naphthenylamino-1.9-anthrapyrimidines which contain the corresponding acylamino groups in the 4-position. The acyl radical may also, be subsequently introduced or the acylation may be carried out in one operation with the replacement of the halogen.

From. 2-halogen-4-aryl-,. alkyl-, aralkylor -cycloalkylamino 1.9 anthrapyrimidines and naphthenylamine, 2-naphthenylamino- 4 -ary1-, -alkyl-, -aralyl lor cycloalkylamino-1.9-anthrapyrimidines are obtained which are also readily soluble in hydrocarbons and artificial compositions and fiuoresce strongly therein. Compounds of this kind which also contain hydroaromatic radicals of alkyl groups of high molecular weight in the joined-on aryl nucleus are especially readily soluble.

By heating 2A dihalogenor 2.4-dihydroxy- 1.9-anthrapyrimidine with at least 2 molecular proportions of naphthenylamine, ZA-dinaphthenylamino- 1.9 -anthrapyrimidines are obtained I which are also extremely powerfully fluorescent I and readily soluble in hydrocarbons.

From the sodium salt of 4-amino-1.9-anthrapyrimidine-Z-selenide and naphthenyl bromide there is obtained 4-amino-1.9-anthrapyrimidine 2-naphthenyl selenide, and from l-amino-LQ- anthrapyrimidine-2-mercapto sodium salt and.

naphthenyl bromide there is obtained 4-amin0- 1.9-anthrapyrimidine-Z-naphthenyl sulphide.

Example 4 dried. The compound dissolves in concentrated sulphuric acid giving a blue coloration and is readily soluble in organic solvents, especially in benzene and hydrocarbons, depending on the nature and amount of the solvent, giving a yellowish to bluish red coloration and a powerful olivetinged yellow fluorescence.

If, instead of Bz2.Bz2'-dihydroxydibenzane throne, the corresponding alky ethers are used, compounds having similar properties are obtained. Triand tetra-hydroxydibenzanthrones may also be caused to react with naphthenyla mine or other amines of this kind.

Example A mixture of 30 parts of leuco-1.4-dihydroxyanthraquinone, 100 parts of isobutyl alcohol and 35 parts of naphthenylamine is heated to boiling while stirring until a sample withdrawn no longer contains unchanged leuco compound. 5 parts of piperidine and 5 parts of copper acetate are then added and air is led through the mixture until the oxidation is completed. The whole is allowed to cool and the 1.4-dinaphthenylaminoanthraquinone obtained in the calculated yield in the form of blue needles is filtered oil by suction. It is very readily soluble in benzene, benzine, paraffin, mineral oils and organic hydrocarbons giving a brilliant blue coloration, and soluble with somewhat more difiiculty in glacial acetic acid, alcohol and dioxane. The color of the solution in concentrated sulphuric acid is yellow.

The same compound can also be obtained by heating 1.4-dihydroxyanthraquinone itself in the presence of a reducing agent, such as sodium hydrosulphite, or leuco-1.4-dihydroxyanthraquinones with naphthenylamine. For example heating of 20 parts of 1.4-dihydroxyanthraquinone, 5 parts of leuco-1. l-dihydroxyanthraquinone and 35 parts of naphthenylamine in 200 parts of butyl alcohol leads to the same final product.

The compound may also be obtained by heating 1.4-dinitro-, 1.4-dimethoxy-, 1-hydroxy-4-methoxy or leuco-l-amino4-hydroxyanthraquinone with naphthenylamine.

From leuco-1.4.5.8-tetrahydroxyanthraquinone and naphthenylamine there is obtained dinaphthenylamino-dihydroxyanthraquinone, and under more active conditions trior tetra-naphthenylaminoanthraquinones. Similarly from 1.5-diamino-4.8dihydroxyanthraquinone and naphthenylamine there is obtained 1.5-diamino-4.8-divnaphthenylaminoanthra uinone, and from 1.5-

diamino-B-hydroxyanthraquinone there is obtained 1.5-diamino-8-naplrthenylaminoanthraquinone.

Other hydroxyanthraquinones may also be caused to react with naphthenylamine, as for example 1-hydroxy-4methylanthraquinone, 1.2-dihydroxyanthraquinone, 1.2.4-trihydroxyanthraquinone, 1.4.5.6-tetrahydroxyanthraquinone, 1- hydroxyanthraquinone-2-carboxylic acid, its esters and amides, 1hydroxyanthraquinone-2-aldehyde and 2.3-dimethyl-5.8-dihydroxyanthraquinone.

Instead of naphthenylamine, omega-amino compounds or omega-monoalkylamino compounds of hexahydrophenylalkanes may also be employed.

Example 6 2 parts of Z-hydroxyanthracene are introduced while stirring at from 140 to 150 C. into 5 parts of naphthenylamine and the mixture is heated for a. short time to boiling. After cooling to about C., the mixture is stirred with about 10 parts of dioxane, filtered by suction when cold and the residue washed with a little dioxane and I methanol. 2-naphthenylaminoanthracene is thus obtained in the form of a yellow crystal powder which dissolves in concentrated sulphuric acid giving a yellow coloration and a strong green fluorescence. It dissolves in organic solvents giving a yellow coloration and, depending on the nature of the solvent, a from blue to green fluorescence; for example the solution in paraflin oil has a pale blue fluorescence, in benzene a greenblue fluorescence, in ether and alcohol a bluegreen fluorescence and in glacial acetic acid a green fluorescence.

From l-hydroxyanthracene there is obtained 1 naphthenylaminoanthracene. From 1 hydroxy-4-methoxyanthracene and naphthenylamine there is obtained 1.4-dinaphthenylaminoanthracene which can also be obtained by the reduction of 1.4-dinaphthenylaminoanthraquinone (see Example 5) with zinc dust and caustic soda solution.

In a similar manner hydroxy compounds of hydrocarbons of high molecular weight and their derivatives react with naphthenylamine to give readily soluble naphthenylamino compounds, as for example hydroxybenzanthracenes, hydroxyacenaphthenes, hydroxypyrenes, hydroxychrysenes, hydroxyperylenes, hydroxyfluoranthenes, hydroxythiphenylenes and hydroxy compounds of heterocyclic compounds such as hydroxycarbazoles, hydroxydiphenylene oxides, lA-dihydroxy 1 azanthraquinones, hydroxyanthraquinoneazines, hydroxyanthraquinoneacridones, hydroxyphenazines, hydroxyperylene dicarboxylic acid imides and -imidazoles, hydroxycoeroxenes, hydroxycoeramidoines and hydroxyanthrapyrimidones.

Instead of naphthenylamine. the amino compounds described in the last paragraph of Example 5 may be used in all cases.

Emample 7 A mixture of 100 parts of perylenetetracarboxylic acid anhydride and 200 parts of naphthenylamine is heated to boiling while stirring until unchanged acid anhydride can no longer be detected. The mixture is then allowed tocool and it is diluted at about 100 C. with 100 parts of dioxane. Perylenetetracarboxylic acid dinaphthenyldi-imide thus separates as .a bluered powder. It is separated in the usual manner and dried. It dissolves in benzene or other hydrocarbons giving a yellow coloration and a strong yellow-green fluorescence. The color of the solution in concentrated sulphuric acid is reddish blue with a vivid red fluorescence.

From halogenperylenetetracarboxylic acid anhydrides and naphthenylamine there are also obtained naphthenylamino derivatives of perylenetetracarboxylic acid dinaphthenyl di imides which are distinguished by even more ready solubility in hydrocarbons.

Similarly from halogenperylenetetracarboxylic acid imides, alkylimides, arylimides or cycloalkylimides with naphthenylamine there are obtained fluorescent, readily soluble compounds.

In a similar manner other peri-dicarboxylic acid anhydrides, as for example anthracene-1.9- dicarboxylic anhydrides, naphthalene-1.4.5.8- tetracarboxylic acid anhydrides, benzanthroneperi-dicarboxylic acid anhydrides, azabenzanthrone-peri-dicarboxylic acid anhydrides, benzperylene dicarboxylic acid anhydrides, naphthalic acid anhydrides and acenaphthalic acid anhydrides react with naphthenylamine. In a corresponding manner from halogen-containing compounds of the said kind there are formed substances which contain the naphthenyl radical in amine-like or imide-like combination.

Example 8 A mixture of 10 parts of 2.4-dibrom-L9-anthrapyrimidone, 34 parts of naphthenylamine and 40 parts of nitrobenzene is heated to boiling in a stirring vessel until initial material can no longer be detected. After cooling to 70 C. the mixture is diluted with 100 parts of dioxane, the compound formed is filtered off by suction after cooling and it is washed with dioxane and methanol. It is a brown resinous mass. The 2.4 dinaphthenyldiamino 1.9 anthrapyrimidone thus obtained dissolves in concentrated sulphuric acid giving a red coloration and a brown-green fluorescence. It is soluble in alcohol with difliculty and in benzene and mineral oils with ease giving a yellow coloration with a strong yellow-green fluorescence.

In a similar manner from dibromanthrapyridones and naphthenylamine there are obtained naphthenylaminoanthrapyridones, from halogencoeramidonines there are obtained naphthenylaminocoeramidonines and from halogen pyrroloanthrones or halogen pyrazolanthrones there are obtained the corresponding naphthenlyamino compounds. In addition to the exchangeable atoms or atomic groups, the said compounds may also contain other radicals, as for example alkyl, aryl, cyano or acyl groups.

Example 9 A mixture of 112 parts of dibrom-allo-msnaphthodianthrone, parts of naphthenylamine, 100 parts of potassium carbonate, 10 parts of copper oxide and 500 parts of nitrobenzene is heated to boiling While stirring until a sample withdrawn no longer contains unchanged initial material. The mixture is then allowed to cool and the naphthenyldiamino-allo-ms-naphthodianthrone precipitated in the form of red-yellow needles is filtered off by suction. It is soluble with ease in benzene and other hydrocarbons giving a yellow-red coloration. The solutions have slight fluorescence.

In a similar manner from dibrompyridino-alloms-naphthodianthrones or from dibromms anthradianthrones, dibrom-aza-ms-anthradianthrones, dibromdibenzanthrones or from halogen compounds of anthraquinones, anthracenes, azaphenanthrenes, anthraquinoneacridones, anthraquinone thioxanthrones, benzanthrones, azabenzanthrones, anthracene-peri di carboxylic acid imides, anthracene-peri-dicarboxylic acid imidazoles, pyrenes, chrysenes, perylenes or other polynuclear hydrocarbons there are obtained the corresponding naphthenylamino compounds.

Example 10 A mixture of 272 parts of 2-hydroxy1.9.4.l0- anthradipyrimidine and 400 parts of naphthenylamine is heated to boiling while stirring. As soon as a sample withdrawn no longer contains hydroxyanthradipyrimidine, the excess of naphthenylamine is distilled off under reduced pressure. Z-naphthenylamino-1.9.4.10-anthradipyrimidine is thus obtained as a yellow powder which dissolves in concentrated sulphuric acid giving a red coloration. It dissolves in benzene or other 3. A high molecular compound corresponding hydrocarbons giving a yellow coloration; the solutions have a green-blue fluorescence. to the general formula The same compound is obtained by using 2- halogen-1.9.4.10-anthradipyrimidines instead of N the Z-hydroxy compound. Similarly the treat- I 5 ment of 4-amino-2-naphthenylamino-1.9-anthrapyrimidine with formamide leads to the same final product.

Instead of anthradipyrimidines there may also be used hydroxy or halogen compounds of anthracene derivatives whichcontain further rings 0 Y joined on in the 1.9.4.10- or 1.9.5.10-position, as Co for example 1.9.4.10- or 1.9.5.10-anthradipyrimi- I dones, -pyridones, -dicoeramidonines or anthrapyrimidinopyrimidones and -pyridones. Also in m Whlch X Stand for the radlca'l 9 h these cases, the second ring may be subsequently carbon conjespondmg to a acld, and joined on For example from zmaphthenyb Y for a hlgh molecular aliphatic hydrocarbon aminol-amino-l.9 anlthrapyrimidine there is radlcalobtained by heating with benzoyl acetic ester the The hlgh molecular compound correspond corresponding Z-naphthenylamino-l Q-anthramg to the formula pyrimidinop-yridone. H What we claim is: 1. A high molecular compound corresponding to the general formula N N (\N NH-naphthenyl (NHX A 1 111 (30 g $111133.

5. A high molecular compound corresponding wherein X stands for the radical of a hydrocarbon corresponding to a naphthenic acid and n for a to the general formula whole number from 1 to 2.

2. A high molecular compound corresponding to the general formula I o X in which the nucleus marked :1: contains up to two groups selected from the class consisting of the I group -NH-X, X being the radical of a hydrocarbon corresponding to a naphthenic acid, in which the nucleus marked x contains a group d th group NH C0 Y, Y being a, high X being the radical of a hydrocarbon molecular aliphatic hydrocarbon radical, at least corresponding to a naphthenic acid, and a group -NH-COY, Y being a high molecular aliphatic hydrocarbon radical.

one of the said groups being a group NH--X.

KARL KOEBERLE.

OTTO SCHLICH'I'ING. 

